EP0929286A1

EP0929286A1 - Compositions for dyeing keratin fibres containing s-oxide-thiazolo-azoles and/or s,s-dioxide-thiazolo-azoles; their use for dyeing as couplers, method of dyeing

Info

Publication number: EP0929286A1
Application number: EP97938944A
Authority: EP
Inventors: Laurent Vidal; Gérard Malle
Original assignee: LOreal SA
Current assignee: LOreal SA
Priority date: 1996-08-26
Filing date: 1997-08-22
Publication date: 1999-07-21
Anticipated expiration: 2017-08-22
Also published as: FR2752524B1; DE69716625D1; WO1998008485A1; JP2000502720A; JP3288387B2; ES2185988T3; FR2752524A1; EP0929286B1; AU4120997A; DE69716625T2; US6340372B1

Abstract

The invention concerns a composition for dyeing keratin fibres, in particular human hair, containing in a medium suitable for dyeing: as coupler at least one compound of formula (I) in which R1 represents in particular hydrogen, halogen, aryloxy, alcoxy, acyloxy, arylthio, alkythio, acetamide; one NRIIIRIV radical with R?III and RIV¿ representing one C¿1?-C4 alkyl....;Za, Zb, Zc represent independently from one another, a nitrogen atom or a carbon atom bearing one R2, R3 or R4 radical; except that: when Za represents a carbon atom bearing a R2 radical, Zb represents a nitrogen atom and Zc represents a carbon atom bearing one R3 radical; when Za represents a nitrogen atom, Zb represents a carbon atom bearing one R4 radical and Zc represents a nitrogen atom; R2, R3 or R4 represent in particular hydrogen; C1-C4 alkyl, linear or branched; aryl optionally substituted....; n is equal to 1 or 2; at least one oxidation base. The invention also concerns the dyeing method using such a composition.

Description

KERATIN FIBER DYEING COMPOSITIONS CONTAINING

S-OXIDE-THIAZOLO-AZOLES AND / OR S, S-DIOXIDE-THIAZOLO-

AZOLES; THEIR USE FOR DYEING AS COUPLERS,

DYEING PROCESS

The subject of the invention is a composition for the oxidation dyeing of keratin fibers, in particular human keratin fibers such as the hair, containing as coupler at least one S-oxide-thiazolazole compound and / or at least an SS-dioxide-thiazolo-azole compound and at least one oxidation base.

It is known to dye keratin fibers and in particular human hair with dye compositions containing oxidation dye precursors, in particular ortho or paraphenylenediamines, ortho or paraaminophenols, heterocyclic compounds, generally called oxidation bases. The precursors of oxidation dyes, or oxidation bases, are colorless or weakly colored compounds which, associated with oxidizing products, can give rise, through an oxidative condensation process, to colored and coloring compounds.

We also know that we can vary the nuances obtained with these oxidation bases by associating them with couplers or color modifiers, the latter being chosen in particular from aromatic metadiamines, metaaminophenols, metadiphenols and certain heterocyclic compounds such as as indole compounds.

The variety of molecules involved in the oxidation bases and couplers, allows obtaining a rich palette of colors.

The so-called "permanent" coloration obtained thanks to these oxidation dyes must moreover satisfy a certain number of requirements. So she must be without drawback from a toxicological point of view, it must make it possible to obtain nuances in the desired intensity and present good resistance to external agents (light, bad weather, washing, permanent waving, perspiration, friction).

The dyes must also make it possible to cover white hair, and finally be the least selective possible, that is to say allow to obtain the smallest possible color differences throughout the same keratin fiber, which can be in fact, differently sensitized (ie damaged) between its tip and its root.

Now, the applicant has now discovered that it is possible to obtain new powerful dyes, not very selective and particularly resistant, capable of generating intense colorings in various shades, by using, as couplers, compounds S -oxide-thiazolazoles and / or S, S-dioxide-thiazolo-azoles in the presence of an oxidation base.

This discovery is the basis of the present invention.

The subject of the invention is a composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing:

- As coupler, at least one S-oxide-thiazolo-azole compound and / or at least one S compound ,. -dioxide-thiazolo-azole of formula (I) and / or at least one of their addition salts with an acid:

in which :

- R., represents a hydrogen atom, a halogen atom such as bromine, chlorine or fluorine; an alkoxy radical (such as for example: methoxy, ethoxy, propyloxy, benzyloxy, methoxyethoxy, phenoxyethoxy, 2-cyanoethoxy, phenethyloxy, p-chlorobenzyloxy, methoxyethylcarbamoylmethoxy); an aryloxy radical (such as, for example: phenoxy, 4-methoxyphenoxy, 4-nitrophenoxy, 4-cyanophenoxy, 4-methanesulfonamidophenoxy, 4-methanesulfonylphenoxy, 3-methylphenoxy, 1-naphthyloxy); an acyloxy radical (such as, for example: acetoxy, propaπoyloxy, benzoyloxy, 2,4-dichlorobenzoyloxy, ethoxyoxaloyloxy, pyruviloyloxy, cinnamoyloxy, myristoyloxy); an arylthio radical (such as for example: phenylthio, 4-carboxy-phenylthio, 2-ethoxy 5-tert-butylphenylthio, 2-carboxyphenylthio,

4-methane-sulfonyl-phenylthio); an alkylthio radical (such as for example: methylthio, ethylthio, propylthio, butylthio, 2-cyanoethylthio, benzylthio, phenethylthio, 2- (diethylamino) ethylthio, ethoxyethylthio, phenoxyethylthio); a heteroarylthio radical (such as for example: 5-phenyl 2,3,4,5-tetrazolylthio, 2-benzothiazolylthio); a heteroaryloxy radical (such as for example: 5-phenyl 2,3,4,5-tetrazolyloxy, 2-benzo-thiazolyloxy); a thiocyano radical; an alkyloxythiocarbonylthio radical (such as dodecyloxythio carbonylthio); a sulfonamido radical (such as benzenesulfonamido, N-ethyltoluene sulfonamido), a pentafluorobutanamido radical; a 2,3,4,5,6-pentafluorobenzamido radical; a pyrazolyl radical; an imidazolyl radical; a triazolyl radical; a tetrazolyl radical; a benzimidazolyl radical; a 1-benzyl 5-ethoxy 3-hydantoinyl radical; a 1-benzyl 3-hydantoinyl radical; 5,5-dimethyl 2,4-dioxo 3-oxazolidinyl; a radical 2-oxy 1, 2-dihydro 1-pyridinyl; an alkylamido radical; an arylamido radical; a radical NR "R ^I where R" and R ^ιv representing identical or different, alkyl, C.-C _4l hydroxyalkyl, C, -C ₄ alkyl, a carboxyl radical, an alkoxycarboxyl radical, an alkyloxycarbonylamino radical, an aryloxycarbonylamino radical, a sulfonyloxy radical such as methanesulfonyloxy, an alkoxycarbonyloxy radical such as methoxycarbonyloxy, ethoxycarbonyloxy or an aryloxycarbonyloxy radical such as phenyloxycarbonyloxy;

- Z _a , Z _b and Z _c represent, independently of each other, a nitrogen atom or else a carbon atom carrying a radical R ₂ , R ₃ or R ₄ ; provided that :

^• when Z _a denotes a carbon atom carrying a radical R ₂ , then Z _b represents a nitrogen atom and Z _c denotes a carbon atom carrying a radical R ₃ ;

^• when Z _a denotes a nitrogen atom, then Z _b represents a carbon atom carrying a radical R ₄ and Z _c denotes a nitrogen atom;

- R ₂ , R ₃ and R ₄ represent, independently of each other, a hydrogen atom; a linear or branched C 1 -C ₂₀ alkyl radical, optionally substituted by 1 or 2 radicals R chosen from the group consisting of halogen, nitro, cyano, hydroxy, alkoxy, aryloxy, amino, alkylamino, acylamino, carbamoyl, sulfonamido, sulfamoyl , imido, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl; an aryl radical (such as phenyl or naphthyl, optionally substituted by 1 or 2 R radicals as defined above); a halogen atom (such as bromine, chlorine or fluorine); an acyl radical; a sulfonyl radical; a sulfinyl radical; a phosphonyl radical, a carbamoyl radical; a sulfamoyl radical; a cyano radical; an amino radical; an alkylamino radical; an acylamino radical; an alkylthio radical; an arylthio radical; an acyloxy radical; a radical carbamoyloxy; a sulfonamido radical; an imido radical; a ureido radical; a sulfamoylamino radical; an alkoxycarbonylamino radical; an aryloxycarbonylamino radical; an alkoxycarbonyl radical; an aryloxycarbonyl radical; a carboxyl radical; a nitro radical; a sulfonyl radical; a hydroxy radical; a mercapto radical or a trifluoromethyl radical;

- n is 1 or 2;

- And at least one oxidation base.

The addition salts with an acid of the compounds of the invention can be chosen in particular from hydrochlorides, hydrobromides, tartrates, tosylates, benzenesulfonates, sulfates, lactates and acetates.

Among the radicals R, of the formula (I) defined above, preferred are the radicals chosen from the group consisting of a hydrogen atom; a C _r C ₄ alkoxy radical; phenoxy; phenoxy substituted by a halogen atom, a C _r C ₄ alkyl, a carboxyl, a trifluoromethyl group, an acyloxy, benzyloxy or C _r C ₄ alkylthio radical; a phenylthio radical; a phenylthio radical substituted by a halogen atom, a C ₁ -C ₄ alkyl, a carboxyl or a trifluoromethyl group; a C _r C ₄ alkylamido radical; a phenylamido radical; a radical NR "^ with R '" and R ^ιv representing, identical or different, a C _r C ₄ alkyl OR a C _r C ₄ hydroxyalkyl; a carboxyl radical; a C ₁ -C ₄ alkoxycarboxyl radical or a halogen atom such as chlorine or bromine.

And even more particularly, the radicals R are chosen, chosen from the group consisting of hydrogen, chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido and dimethylamino. Among the radicals R ₂ , R ₃ or R ₄ of formula (I), preferred are the radicals chosen from the group consisting of a hydrogen atom; a linear or branched C _r C ₄ alkyl radical; aryl; aryl substituted by a halogen atom, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group, an amino group; cyano; nitro; acylamino; arylamino; alkylthio such as methylthio, ethylthio; arylthio such as phenylthio; carbamoyl such as N-ethylcarbamoyl; sulfonyl such as methylsulfonyl; alkoxycarbonyl such as methoxycarbonyl, ethoxycarbonyl; aryloxycarbonyl such as phenoxycarbonyl; acyl such as acetyl or propionyl.

And even more particularly, the radicals R ₂ , R ₃ or R ₄ of the formula (I) chosen from the group consisting of a hydrogen atom are preferred; a linear or branched O, -0 ₄ alkyl radical (such as methyl, ethyl, isopropyl); phenyl; phenyl substituted by a halogen atom, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group, an amino group.

Among the preferred compounds of formula (I) of the invention, mention may be made of those chosen from the group consisting of:

i) the compounds of formula (la) below:

in which R represents a hydrogen or chlorine atom; R ₂ and R ₃ denote, independently of one another, a hydrogen atom, a methyl radical, an ethyl radical or a phenyl radical; n is 1 or 2. i) the compounds of formula (Ib) below:

in which R represents a hydrogen or chlorine atom; R ₄ denotes a hydrogen atom, a methyl radical, an ethyl radical, a phenyl radical, a trifluoromethyl radical or a cyano radical; n is 1 or 2.

Among the compounds of formula (la) of the invention which are particularly preferred, mention may be made of those chosen from the group consisting of:

- 3-nitro-5-methyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- S, S-3-nitro-5-methyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- 3-amino-5-methyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- S, S-3-amino-5-methyl-7-oxothiazolo [2,3-e] -imidazole dioxide; - 3-amiπo-5-phenyl ~ 7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- 3-nitro-5-phenyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- S, S-3-nitro-5-methyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- S, S-3-amino-5-phenyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- 3-phenyl-5-methyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

Among the particularly preferred compounds of formula (Ib) of the invention, mention may be made of those chosen from the group consisting of:

- 7-oxothiazolo- [3,2-b] -thazole sulfoxide;

- 4-methyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide; - 4-ethyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-isopropyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-propyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide; - 4-trιfluoromethyI-7-oxothιazolo- [3,2-b] -trιazcHe sulfoxide,

- 4-phenyl-7-oxothιazolo- [3,2-b] -trιazole sulfoxide

- 7-oxothιazolo- [3,2-b] -tπazole sulfoxide,

- S, S-oxide of 7-oxothιazolo- [3,2-b] -tπazole, - S, S-oxide of 4-methyl-7-oxothιazolo- [3,2-b] -trιazole,

- S, S-4-phenyl-7-oxide-oxothιazolo- [3,2-b] -trιazole oxide,

The compounds of formula (I) of the present invention, their synthetic intermediates and their methods of preparation are described in the following documents

- JP 07 09 84 89,

- Khim Geterotsilk Soedin, 1967, p 93, - J Prakt Chem, 318, 1976, p 12,

- Indian J Heterocycl Chem 1995, 5 (2), p 135, - Acta Pol Pharm 1995, 52 (5), 415,

- Heterocycl Commun 1995, 1 (4), 297,

- Arch Pharm (Weinheim, Ger), 1994, 327 (12), 825

- J Am Chem Soc, 79, 1957, 2188,

- Liebigs Ann Chem, 744, 1971, 51, - J Chem Soc, 1949, 1160,

- Bull Chem, Soc Chim Belg, 75, 1966, 358

The compound or compounds of formula (I) in accordance with the invention preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight

The nature of the oxidation base or bases which can be used in the dye composition according to the invention is not critical This or these oxidation bases are preferably chosen from paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols, heterocyclic bases, and their addition salts with an acid.

Among the paraphenylenediamines which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of the compounds corresponding to the following formula (II), and their addition salts with an acid:

wherein: - R ₅ represents a hydrogen atom, an alkyl radical with C, -C ₄ monohydroxyalkyl, C _r -C ₄ polyhydroxyalkyl, C ₂ -C ₄ alkoxy or (C _r C ₄₎ alkyl (C ₁ - C ₄ ),

- R ₆ represents a hydrogen atom, a C _r C ₄ alkyl, C, -C ₄ monohydroxyalkyl or C ₂ -C ₄ polyhydroxyalkyl radical, - R ₇ represents a hydrogen atom, a halogen atom such as a chlorine atom, an alkyl radical with C, -C ₄ alkyl, sulfo, carboxy, monohydroxyalkyl, C, -C ₄ hydroxyalkoxy or C _r C _4,

- R ₈ represents a hydrogen atom or a CC ₄ alkyl radical.

In formula (II) above, and when R ₇ is different from a hydrogen atom, then R ₅ and R ₆ preferably represent a hydrogen atom and R ₇ is preferably identical to R ₈ , and when R ₇ represents a halogen atom, then R ₅ , R ₆ and. _B preferably represent a hydrogen atom.

Among the paraphenylenediamines of formula (II) above, there may be mentioned more particularly paraphenylenediamine, paratoluylenediamine, 2-isopropyl paraphenylene diamine, 2-β-hydroxyethyl paraphenylenediamine, 2-β-hydroxyethyloxy para-phenylenediamine, 2,6-dimethyl paraphenylenediamine, 2,6-diethyl paraphenylene diamine, 2,3-dimethyl paraphenylenediamine, N, N-bis- (β-hydroxyethyl) para- phenylenediamine, 4-amino 1- (β-methoxyethyl) amino benzene, 2-chloro para-phenylenediamine, and their addition salts with an acid.

Among the bis-phenylalkylenediamines which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of the compounds corresponding to the following formula (III), and their addition salts with an acid:

in which :

- Q, and Q ₂ , identical or different, represent a hydroxyl radical or NHR ₁₂ in which R ₁₂ represents a hydrogen atom or a C ₁ -C ₄ alkyl radical,

- R ₉ represents a hydrogen atom, an alkyl radical in C _r -C ₄ monohydroxyalkyl, C _r -C ₄ polyhydroxyalkyl, C ₂ -C ₄ aminoalkyl or C, -C ₄ alkyl which remains the amino may be substituted,

R ₁₀ and R _{11 (} identical or different, represent a hydrogen or halogen atom or a C ₄ -C ₄ alkyl radical,

- W represents a radical taken from the group consisting of the following radicals:

- (CH ₂ ) _n -; - (CH ₂ ) _m -0- (CH ₂ ) -; - (CH ₂ ) _m -CHOH- (CH ₂ ) - and

- (CH ₂ ) - N- (CH ₂ ) -; CH ₃ in which n is an integer between 0 and 8 inclusive and m is an integer between 0 and 4 inclusive. Among the bis-phenylalkylenediamines of formula (III) above, there may be mentioned more particularly N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino 2-propanol, N, N'-bis- (β-hydroxyethyl) N, N'-bis- (4'-aminophenyl) ethylenediamine, N, N'-bis- (4-aminophenyl) tetramethylenediamine, N. N'-bis- (β-hydroxyethyl) N, N'-bis- (4-aminophenyl) tetramethylenediamine, N, N'-bis- (4-methylaminophenyl) tetramethylenediamine, N, N'-bis- (ethyl) N, N'-bis- (4'-amino, 3'-methylphenyl) ethylenediamine, and their acid addition salts.

Among these bis-phenylalkylenediamines of formula (III), N, N'-bis- (β- hydroxyethyl) N, N'-bis- (4'-aminophenyl) 1, 3-diamino propanol or one of its salts addition with an acid are particularly preferred.

Among the paraaminophenols which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of the compounds corresponding to the following formula (IV), and their addition salts with an acid:

wherein: - R ₁₃ represents a hydrogen atom, an alkyl radical in C _r -C ₄ monohydroxyalkyl, C _r C ₄ alkoxy (C ₁ -C ₄₎ alkyl (C ₁ -C ₄₎ alkylamino or C -C ₄ alkyl, - R ₁₄ represents a hydrogen or fluorine atom, a ra ^d ical C, -C ₄ monohydroxyalkyl, C, -C ₄ polyhydroxyalkyl, C ₂ -C ₄ aminoalkyl, C _r C ₄ cyanoalkyl, C _r -C ₄ alkoxy or (C ₁ -C ₄₎ alkyl (C ₁ -C ₄₎ alkyl, provided that at least one of R ₁₃ or R ₁₄ represents a hydrogen atom. Among the paraaminophenols of formula (IV) above, mention may more particularly be made of paraaminophenol, 4-amiπo 3-methyl phenol, 4-amino 3-fluoro phenol, 4-amino 3-hydroxymethyl phenol, 4- amino 2-methyl phenol, 4-amino 2-hydroxymethyl phenol, 4-amino 2-methoxymethyl phenol, 4-amino 2-aminomethyl phenol, 4-amino 2- (β-hydroxyethyl aminomethyl) phenol, and their salts addition with an acid.

Among the ortho-aminophenols which can be used as oxidation bases in the dye composition according to the invention, there may be mentioned in particular 2-amino phenol, 2-amino 1-hydroxy 5-methyl benzene, 2-amino 1- hydroxy 6-methyl benzene, 5-acetamido 2-amino phenol, and their addition salts with an acid.

Among the heterocyclic bases which can be used as oxidation bases in the dye composition according to the invention, mention may in particular be made of pyridine derivatives, pyrimidine derivatives, pyrazole derivatives, and their addition salts with an acid.

Among the pyridine derivatives, mention may more particularly be made of the compounds described for example in patents GB 1 026 978 and GB 1 153 196, such as 2,5-diaminopyridine, and their addition salts with an acid.

Among the pyrimidine derivatives, mention may more particularly be made of the compounds described for example in the German patents DE 2 359 399 or Japanese JP 88-169 571 and JP 91-333 495, such as 2,4,5,6-tetra-aminopyrimidine , 4-hydroxy 2,5,6-triamino-pyrimidine, and their acid addition salts.

Among the pyrazole derivatives, mention may more particularly be made of the compounds described in patents DE 3 843 892, DE 4 133 957 and patent applications WO 94/08969 and WO 94/08970 such as 4,5-diamino 1-methyl pyrazole, 3,4-diamino pyrazole and 1- (4'-chlorobenzyl) -4,5-diaminopyrazole, and their addition salts with an acid.

According to the invention, the oxidation base (s) preferably represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 6% by weight approximately of this weight.

The dye composition according to the invention may also contain one or more additional couplers different from the compounds of formula (I) and / or one or more direct dyes so as to vary or enrich in reflections the shades obtained with the oxidation bases.

The additional couplers which can be used in the composition according to the invention can be chosen from the couplers conventionally used in oxidation dyeing and among which there may be mentioned in particular metaphenylenediamines, meta-aminophenols, metadiphenols and heterocyclic couplers such as by example indole derivatives, indoline derivatives, and their addition salts with an acid.

These couplers can in particular be chosen from 2-methyl 5-amino phenol, 5-N- (β-hydroxyethyl) amino 2-methyl phenol, 3-amino phenol, 1, 3-dihydroxybenzene, 1, 3- dihydroxy 2-methyl benzene, 4-chloro, 3-dihydroxy benzene, 2,4-diamino l- (β-hydroxyethyloxy) benzene, 2-amino 4- (β-hydroxyethylamino) 1-methoxy benzene, 1, 3-diamino benzene, 1, 3-bis- (2,4-diaminophenoxy) propane, sesamol, α-naphthol, 6-hydroxy ihiole, 4-hydroxy indole, 4-hydroxy N-methyl indole , 6-hydroxy indoline, and their acid addition salts.

When present, these additional couplers preferably represent from 0.0005 to 5% by weight approximately of the total weight of the dye composition, and even more preferably from 0.005 to 3% by weight approximately of this weight. The addition salts with an acid of the oxidation base (s) and / or additional couplers which can be used in the dye composition of the invention are in particular chosen from hydrochlorides, hydrobromides, sulphates and tartrates, lactates and acetates.

The medium suitable for dyeing (or support) generally consists of water or of a mixture of water and at least one organic solvent to dissolve the compounds which are not sufficiently soluble in water. As organic solvent, mention may, for example, be made of lower C _r C ₄ alcohols, such as ethanol and isopropanol; glycerol; glycols and glycol ethers such as 2-butoxyethanol, propylene glycol, propylene glycol monomethyl ether, monoethyl ether and diethylene glycol monomethyl ether, as well as aromatic alcohols such as benzyl alcohol or phenoxyethaπol, analogues and their mixtures.

The solvents may be present in proportions preferably of between 1 and 40% by weight approximately relative to the total weight of the dye composition, and even more preferably between 5 and 30% by weight approximately.

The pH of the dye composition according to the invention is generally between 3 and 12. It can be adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers.

Among the acidifying agents, there may be mentioned, by way of example, mineral or organic acids such as hydrochloric acid, orthophosphoric acid, carboxylic acids such as tartaric acid, citric acid, lactic acid, sulfonic acids. Among the basifying agents, there may be mentioned, by way of example, ammonia, alkali carbonates, alkanolamines such as mono-, di- and tethanolamines as well as their derivatives, sodium or potassium hydroxides and compounds of following formula (V)

R 15 "17

\ /

N - R - N (V)

/ \

R 16 R,

in which R is a propylene residue optionally substituted by a hydroxyl group or an alkyl radical in CC ₄ , R ₁₅ , R ₁₆ , R ₁₇ and R _18l identical or different, represent a hydrogen atom, an alkyl radical in C, - C ₄ hydroxyalkyl or C l -C ₄

The dye composition according to the invention may also contain various adjuvants conventionally used in compositions for dyeing the hair, such as anionic, cationic, non-lonic, amphoteric, zwitterπonic agents or mixtures thereof, anionic, cationic polymers , non-ionic, amphoteric, zwitterπonic or their mixtures, mineral or organic thickening agents, antioxidant agents, penetration agents, sequestering agents, perfumes, buffers, dispersing agents, conditioning agents such as for example silicones, film-forming agents, preserving agents, opacifying agents

Of course, those skilled in the art will take care to choose the optional compound (s) mentioned above, in such a way that the advantageous properties intrinsically attached to the dye composition according to the invention are not, or not substantially, altered. by the planned addition (s) The dye composition according to the invention can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair.

A subject of the invention is also the use of the compounds of formula (I) above, as a coupler, in combination with at least one oxidation base for the oxidation dyeing of keratin fibers and in particular of keratin fibers human such as hair.

Another subject of the invention is a process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, using the dye composition as defined above.

According to this process, at least one dye composition as defined above is applied to the fibers, the color being revealed at acidic, neutral or alkaline pH using an oxidizing agent which is added just at the time of use. the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially separately.

According to a particularly preferred embodiment of the dyeing process according to the invention, the dye composition described above is mixed at the time of use with an oxidizing composition containing, in a medium suitable for dyeing, Look for an oxidizing agent present in an amount sufficient to develop a color. The mixture obtained is then applied to the keratin fibers and left to stand for 3 to 50 minutes approximately, preferably 5 to 30 minutes approximately, after which it is rinsed, washed with shampoo, rinsed again and dried. The oxidizing agent present in the oxidizing composition as defined above can be chosen from the oxidizing agents conventionally used for the oxidation dyeing of keratin fibers, and among which mention may be made of hydrogen peroxide, urea, alkali metal bromates, persalts such as perborates and persulfates. Hydrogen peroxide is particularly preferred.

The pH of the oxidizing composition containing the oxidizing agent as defined above is such that after mixing with the dye composition, the pH of the resulting composition applied to the keratin fibers preferably varies between 3 and 12 approximately and even more preferably between 5 and 11. It is adjusted to the desired value by means of acidifying or basifying agents usually used in dyeing keratin fibers and as defined above.

The oxidizing composition as defined above may also contain various adjuvants conventionally used in compositions for dyeing the hair and as defined above.

The composition which is finally applied to the keratin fibers can be in various forms, such as in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular human hair. .

Another object of the invention is a device with several compartments or "kit" for dyeing or any other packaging system with several compartments, a first compartment of which contains the dye composition as defined above and a second compartment of which contains the oxidizing composition. as defined above. These devices can be equipped with a means enabling the desired mixture to be delivered to the hair, such as the devices described in patent FR-2,586,913 in the name of the applicant.

EXAMPLES

EXAMPLES 1 AND 2 OF THE DYEING PROCESS IN AN ALKALINE MEDIUM

The following dye composition, in accordance with the invention, was prepared (contents in grams):

- 3-nitro-5-methyl-7- sulfoxide

-oxothiazolo [2,3-e] imidazole (coupler) ( ^* ) 0.645 g

- 4- (2-methoxyethylamino) aniline (oxidation base) 0.498 g - Ethanol 20.0 g

- Ammonia at 20% NH ₃ 10.0 g

- Sodium meta bisulfite 0.228 g

- Sequestering agent q.s

- Demineralized water qs 100 g

(*) The sulfoxide of 3-nitro-5-methyl-7-oxothiazolo [2,3-e] imidazole is synthesized according to the process described in patent JP 07098489 and the articles Khim. Geterotsilk. Soedin, 1967, p. 93 and J. Am. Chem. Soc, 79, 1957, 2188 -;

EXAMPLE 1

At the time of use, the dye composition was mixed with an equal amount by weight of an aqueous solution of ammonium persulfate to 6.10- ³ mole%.

The mixture obtained was applied for 30 minutes to locks of natural gray hair containing 90% white hairs, permanent or not, at a rate of 10 g per 1 g of hair. After rinsing, washing with a standard shampoo and drying the locks, powerful colors are obtained, which are not very selective in the range of reds.

EXAMPLE 2

At the time of use, the dye composition was mixed with an equal amount by weight of an aqueous solution of hydrogen peroxide at 20 volumes.

EXAMPLES 3 AND 4 OF THE NEUTRAL DYEING PROCESS

- 3-nitro-5-methyl-7- sulfoxide

-oxothiazolo [2,3-e] imidazole (coupler) 0.645 g

- 4- (2-methoxyethylamino) aniline (oxidation base) 0.498 g

- Ethanol 20.0 g - Buffer K ₂ HP0 ₄ / KH ₂ P0 ₄ (1.5 M / 1 M) 10 g

- Sodium metabisulfite 0.228 g

- Sequestering agent q.s

- Demineralized water qs 100 g

EXAMPLE 3

At the time of use, the dye composition was mixed with an equal amount by weight of an aqueous solution of ammonium persulfate at 6.10 ³ mol%.

The mixture obtained was applied for 30 minutes to locks of natural gray hair containing 90% white hairs, permanent or not, at a rate of 10 g per 1 g of hair. After rinsing, washing with a standard shampoo and drying the locks, powerful colors are obtained, which are not very selective in the range of reds. EXAMPLE 4

Claims

1. Composition for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that it comprises, in a medium suitable for dyeing:

- As coupler, at least one S-oxide-thiazolo-azole compound and / or at least one S, S-dioxide-thiazolo-azole compound of formula (I) and / or at least one of their salts d 'addition with an acid:

in which :

- R, represents: a hydrogen atom; a halogen atom; an alkoxy radical; an aryloxy radical; an acyloxy radical; an arylthio radical; an alkylthio radical; a heteroarylthio radical; a heteroaryloxy radical; a thiocyano radical; an alkyloxythiocarboπylthio radical; a sulfonamido radical; a pentafluorobutanamido radical; a 2,3,4,5,6-pentafluorobenzamido radical; a pyrazolyl radical; an imidazolyl radical; a triazolyl radical; a tetrazolyl radical; a benzimidazolyl radical; a 1-benzyl 5-ethoxy 3-hydantoinyl radical; a 1-benzyl 3-hydantoinyl radical; 5,5-dimethyl 2,4-dioxo 3-oxazolidinyl; a 2-oxy 1,2-dihydro 1-pyridinyl radical; an alkylamido radical; an arylamido radical; a radical NR "'R ^I where R" and R ^ιv representing identical or different, a C _r -C ₄ hydroxyalkyl, C _r C _4l a carboxyl radical, an alkoxycarboxyl radical, an alkyloxycarbonylamino radical, a aryloxycarbonylamino , a sulfonyloxy radical, an alkoxycarbonyloxy radical or an aryloxycarbonyloxy radical; - Z _a , Z _b and Z _c represent, independently of each other, a nitrogen atom or else a carbon atom carrying a radical R ₂ , R ₃ or R ₄ ; provided that :

• when Z _a denotes a nitrogen atom, then Z _b represents a carbon atom carrying a radical R ₄ and Z _c denotes a nitrogen atom;

- R ₂ , R ₃ and R ₄ represent, independently of each other, a hydrogen atom; a linear or branched C ₁ -C ₂₀ alkyl radical, optionally substituted by 1 or 2 radicals R chosen from the group consisting of halogen, nitro, cyano, hydroxy, alkoxy, aryloxy, amino, alkylamino, acylamino, carbamoyl, sulfonamido , sulfamoyl, imido, alkylthio, arylthio, aryl, alkoxycarbonyl, acyl; an aryl radical, optionally substituted with 1 or 2 radicals R as defined above; a halogen atom; an acyl radical; a sulfonyl radical; a sulfinyl radical; a phosphonyl radical, a carbamoyl radical; a sulfamoyl radical; a cyano radical; an amino radical; an alkylamino radical; an acylamino radical; an alkylthio radical; an arylthio radical; an acyloxy radical; a carbamoyloxy radical; a sulfonamido radical; an imido radical; a ureido radical; a sulfamoylamino radical; an alkoxycarbonylamino radical; an aryloxycarbonylamino radical; an alkoxyoarbonyl radical; an aryloxycarbonyl radical; a carboxyl radical; a nitro radical; a sulfonyl radical; a hydroxy radical; a mercapto radical; a trifluoromethyl radical;

n is 1 or 2; - And at least one oxidation base.

2. Composition according to Claim 1, characterized in that the radicals R, of formula (I) are chosen from the group consisting of a hydrogen atom; C _r C ₄ alkoxy; phenoxy; phenoxy substituted by a halogen atom, a C ₄ -C ₄ alkyl, a carboxyl, a trifluoromethyl group, an acyloxy, benzyloxy or C ₁ -C ₄ alkylthio radical; a phenylthio radical; a phenylthio radical substituted by a halogen atom, a C _r C ₄ alkyl, a carboxyl, a trifluoromethyl group; a C _r C ₄ alkylamido radical; a phenylamido radical; a radical NR '"R ^IV with R'" and R ^ιv representing, identical or different, a CC ₄ alkyl, a C ₄ -C hydroxyalkyl; a carboxyl radical; a C 1 -C ₄ alkoxycarboxyl radical or a halogen atom.

3. Composition according to claim 1 or 2, characterized in that the radicals R, of formula (I) are chosen from the group consisting of hydrogen; chlorine; ethoxy; phenoxy; benzyloxy; acyloxy; acetamido; dimethylamino.

4. Composition according to any one of claims 1 to 3, characterized in that the radicals R ₂ , R ₃ or R ₄ of the formula (I) are chosen from the group consisting of a hydrogen atom; a linear or branched C _r C ₄ alkyl radical; aryl; aryl substituted by halogen, methoxy radical, nitro group, cyano group, trifluoromethyl group, amino group; cyano; nitro; acylamino; arylamino; alkylthio; arylthio; carbamoyl; sulfonyl; alkoxycarbonyl; aryloxycarbonyl; acyle.

5. Composition according to Claim 4, characterized in that the radicals R ₂ , R ₃ or R ₄ of the formula (I) are chosen from the group consisting of a hydrogen atom; a linear or branched C _r C ₄ alkyl radical; phenyl; phenyl substituted by a halogen, a methoxy radical, a nitro group, a cyano group, a trifluoromethyl group, an amino group.

6. Composition according to any one of claims 1 to 5, characterized in that the compounds of formula (I) are chosen from the group consisting of:

i) the compounds of formula (la) below:

in which R represents a hydrogen or chlorine atom; R ₂ and R ₃ denote, independently of one another, a hydrogen atom, a methyl radical, an ethyl radical or a phenyl radical; n is 1 or 2.

i) the compounds of formula (Ib) below:

in which R. represents a hydrogen or chlorine atom; R ₄ denotes a hydrogen atom, a methyl radical, an ethyl radical, a phenyl radical, a trifluoromethyl radical or a cyano radical; n is 1 or 2.

7. Composition according to claim 6, characterized in that the compounds of formula (la) are chosen from the group consisting of:

- 3-nitro-5-methyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- S, S-3-nitro-5-methyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- 3-amino-5-methyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- S, S-3-amino-5-methyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- 3-amino-5-phenyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- 3-nitro-5-phenyl-7-oxothiazolo [2,3-e] -imidazole sulfoxide;

- S, S-3-nitro-5-methyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- S, S-3-amino-5-phenyl-7-oxothiazolo [2,3-e] -imidazole dioxide;

- 3-phenyl-5-methyl-7-oxothiazolo [2,3-ej-imidazole sulfoxide;

8. Composition according to claim 6, characterized in that the compounds of formula (Ib) are chosen from the group consisting of:

- 7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-methyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-ethyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-isopropyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-propyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-trifluoromethyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 4-phenyl-7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- 7-oxothiazolo- [3,2-b] -triazole sulfoxide;

- S, S-dioxide of 7-oxothiazolo- [3,2-b] -triazole;

- S, S-4-methyl-7-oxothiazolo- [3,2-b] -triazole dioxide;

- 4-phenyl-7-oxothiazolo- [3,2-b] -triazole S.S-dioxide.

9. Composition according to any one of the preceding claims, characterized in that the acid addition salts of the compounds of formula (I) are chosen from hydrochlorides, hydrobromides, sulfates, tartrates, benzenesulfonates, lactates, tosylates and acetates.

10. Composition according to any one of the preceding claims, characterized in that the compound or compounds of formula (I) represent from 0.0005 to 12% by weight of the total weight of the dye composition.

1 1. Composition according to claim 10, characterized in that the compound or compounds of formula (I) represent from 0.0005 to 12% by weight of the total weight of the dye composition.

12. Composition according to any one of the preceding claims, characterized in that the oxidation base or bases are chosen from paraphenylenediamines, bis-phenylalkylenediamines, paraaminophenols, ortho-aminophenols, heterocyclic bases, and their salts addition with an acid.

13. Composition according to any one of the preceding claims, characterized in that the oxidation base or bases represent from 0.0005 to 12% by weight approximately of the total weight of the dye composition.

14. Composition according to Claim 13, characterized in that the oxidation base or bases represent from 0.005 to 6% by weight approximately of the total weight of the dye composition.

15. Composition according to any one of the preceding claims, characterized in that it also contains one or more additional couplers different from the compounds of formula (I) and / or one or more dyes called ^c ts.

16. Composition according to any one of the preceding claims, characterized in that the medium suitable for dyeing (or support) consists of water or of a mixture of water and at least one chosen organic solvent among the lower C - C ₄ alcohols, glycerol, glycols and glycol ethers, aromatic alcohols, analogues and their mixtures.

17. Composition according to any one of the preceding claims, characterized in that it has a pH of between 3 and 12.

18. Composition according to any one of the preceding claims, characterized in that it is in the form of liquids, creams, gels, or in any other form suitable for dyeing keratin fibers, and in particular hair. humans.

19. Use of the compounds of formula (I) or their addition salts with an acid as defined in any one of claims 1 to 8, as couplers in compositions for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, in combination with at least one oxidation base.

20. Process for the oxidation dyeing of keratin fibers and in particular human keratin fibers such as the hair, characterized in that at least one dye composition as defined in any one of claims 1 is applied to these fibers at 18, the color being revealed at acid, neutral or alkaline pH using an oxidizing agent which is added just at the time of use to the dye composition or which is present in an oxidizing composition applied simultaneously or sequentially with separately.

21. The method of claim 20, characterized in that the oxidizing agent is chosen from hydrogen peroxide, urea peroxide, alkali metal bromates, persalts such as perborates and persulfates.

22. Device with several compartments, or "kit" for dyeing with several compartments, a first compartment of which contains a dye composition as defined in any one of claims 1 to 18 and a second compartment of which contains an oxidizing composition.